A general problem in carbohydrate chemistry is the lack of selective reactions of unprotected carbohydrates. Usually a protection-deprotection strategy is employed, which can result in long and therefore very ineffective synthetic routes. We were inspired by a report from Waymouth et al. on the selective oxidation of glycerol to dihydroxy acetone [1] and we envisioned that this catalytic system may also selectively oxidize carbohydrates. A test reaction of methyl a glucopyranoside revealed that indeed the oxidation is selective, and by NMR studies it became clear that the oxidation takes place at C3. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/239nm/uploads/8162_acs_figure.jpg' alt='' />Apart from methyl a-D-glucopyranoside the oxidation has also shown to be selective for methyl �-D-glucopyranoside and methyl N-acetyl a-D-glucosaminepyranoside which all were selectively oxidized at C3 and isolated in high yield and purity on gram scale. Several examples will be shown including two disaccharides, which all were oxidized at C3 with good selectivities and moderate to good isolated yields. The identity of the all keto-sugars was established by thorough NMR-studies.It will also be shown how this method can be applied in the synthesis of methyl allose and aminosaccharides and for the modification of complex natural products.[1] Painter, R.M., Pearson, D.M. and Waymouth, R.M., Angew. Chem. Int. Ed. 49 (2010) 9456-9459 E-mail: manuel.jager@rug.nlwww: http://www.rug.nl/research/bio-organic-chemistry/minnaard/

Selective oxidation of glycosides

246th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.